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Synthesis method for 1,5-ketonic ester compound under catalyzing of inorganic base

A synthesis method and compound technology, applied in the preparation of organic compounds, chemical instruments and methods, organic chemistry, etc., can solve problems such as inability to achieve wide application and actual production, further application restrictions, harsh reaction conditions, etc., to achieve cost savings, The effect of reducing production costs and mild reaction conditions

Inactive Publication Date: 2015-11-18
SOUTHWEST UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0019] 1) The product has only a moderate yield, and toxic reagents are used in the reaction process, and the reaction conditions are harsh, so that its wide application and actual production cannot be realized;
[0020] 2) These methods are usually catalyzed by noble or toxic metals and strong oxidants, which also limits their further applications;
[0021] 3) There are many side reactions, and the by-products are useless

Method used

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  • Synthesis method for 1,5-ketonic ester compound under catalyzing of inorganic base
  • Synthesis method for 1,5-ketonic ester compound under catalyzing of inorganic base
  • Synthesis method for 1,5-ketonic ester compound under catalyzing of inorganic base

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] The preparation of embodiment 1, ethyl 4-benzoyl butyrate (compound III-1)

[0046]

[0047] In the 20mL reaction tube, add compound dibenzoylmethane 112mg (0.5mmol), K 2 CO 3 7 mg (0.025 mmol), 109 μL (1 mmol) of ethyl acrylate and 2 mL of ethanol, stirred at 85 ° C for 2 hours under temperature control, cooled to room temperature (18 ~ 25 ° C), transferred to a 25 mL small flask, and placed on a rotary evaporator Spin off the solvent, and then use neutral alumina to pass through the column. The developer used is petroleum ether: ethyl acetate = 15:1 ~ 5:1, and the compound III-1108 mg is obtained, with a yield of 98%; a colorless oily liquid; 1 HNMR (600MHz, CDCl 3, 25℃, TMS): δ=7.97(d, J=7.6Hz, 2H), 7.56(t, J=7.4Hz, 1H), 7.46(t, J=7.6Hz, 2H), 4.14(q, J= 7.1Hz, 2H), 3.06(t, J=7.2Hz, 2H), 2.43(t, J=7.2Hz, 2H), 2.08(p, J=7.2Hz, 2H), 1.26ppm(t, J=7.1 Hz,3H); 13 CNMR (151MHz, CDCl 3, 25℃, TMS) δ=199.45(s), 173.26(s), 136.96(s), 133.06(s), 128.62(s), 128.06(s), 60...

Embodiment 2

[0048] The preparation of embodiment 2,4-p-methoxybenzoyl ethyl butyrate (compound III-2)

[0049]

[0050] Add compound 1,3-bis(4-methoxyphenyl)1,3-propanedione 142mg (0.5mmol), K 2 CO 3 7 mg (0.025 mmol), 109 μL (1 mmol) of ethyl acrylate and 2 mL of ethanol, stirred at 85 ° C for 2 hours under temperature control, cooled to room temperature (18 ~ 25 ° C), transferred to a 25 mL small flask, and placed on a rotary evaporator The solvent was spun off, and then passed through the column with neutral alumina, and the developer used was petroleum ether: ethyl acetate = 25:1-8:1 to obtain 175 mg of compound III-2, with a yield of 70%; the melting point of the white solid was 56-59°C; 1 HNMR (600MHz, CDCl 3, 25℃, TMS) δ=7.95(d, J=8.6Hz, 2H), 6.93(d, J=8.6Hz, 2H), 4.14(q, J=7.1Hz, 2H), 3.86(s, 3H), 2.99(t, J=7.2Hz, 2H), 2.42(t, J=7.2Hz, 2H), 2.06(p, J=7.2Hz, 2H), 1.25ppm(t, J=7.1Hz, 3H); 13 CNMR (151MHz, CDCl 3, 25℃, TMS) δ=197.99(s), 173.27(s), 163.47(s), 130.27(s), 130.0...

Embodiment 3

[0051] The preparation of embodiment 3, ethyl 4-pyridineformyl butyrate (compound III-3)

[0052]

[0053] Add compound 1,3-bis(2-pyridyl)1,3-propanedione 113mg (0.5mmol), K 2 CO 3 7 mg (0.025 mmol), 109 μL (1 mmol) of ethyl acrylate and 2 mL of ethanol, stirred at 85 ° C for 2 hours under temperature control, cooled to room temperature (18 ~ 25 ° C), transferred to a 25 mL small flask, and placed on a rotary evaporator The solvent was spun off, and then neutral alumina was used to pass through the column. The developer used was petroleum ether: ethyl acetate = 10:1 ~ 3:1 to obtain 166 mg of compound III-3 with a yield of 75%; 1 HNMR (600MHz, CDCl 3, 25℃, TMS)) δ=8.67(d, J=4.7Hz, 1H), 8.04(d, J=7.8Hz, 1H), 7.84(t, J=7.7Hz, 1H), 7.50–7.44(m, 1H), 4.14(q, J=7.1Hz, 2H), 3.29(t, J=7.3Hz, 2H), 2.44(t, J=7.4Hz, 2H), 2.08(p, J=7.3Hz, 2H) ,1.25ppm(t,J=7.1Hz,3H); 13 CNMR (151MHz, CDCl 3, 25℃, TMS) δ=201.08(s), 173.20(s), 153.33(s), 148.91(s), 136.83(s), 127.06(s), 121.69(s), 6...

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Abstract

The invention discloses a synthesis method for a 1,5-ketonic ester compound under catalyzing of inorganic base. The synthesis method comprises the following steps: taking a compound of the general formula I as a raw material, taking inorganic base as a catalyst, controlling the temperature of an alcohol solvent to be 60 to 100 DEG C, and adding a compound of the general formula II for tertiary series reaction of Michael addition, reverse Claisen condensation and ester interchange, so as to obtain the 1,5-ketonic ester compound of the general formula III. The synthesis method has the advantages that the synthesis cost of the 1,5-ketonic ester compound is greatly reduced; the reaction conditions are mild; use of precious and / or poisonous metal and storge oxidant are avoided; the yield of 1,5-ketonic ester compound is greatly improved; industrial synthesis of the 1,5-ketonic ester compound can be realized.

Description

technical field [0001] The invention belongs to the field of chemical synthesis, and in particular relates to a synthesis method of inorganic base-catalyzed 1,5-keto ester compounds. Background technique [0002] The structures of 1,5-dicarbonyl compounds are widely found in medicinal chemistry, functional materials and natural products. Moreover, they are often used in the synthesis of heterocyclic and aromatic compounds, and they are also prochiral molecules for the synthesis of various chiral compounds. So far, there are not many synthetic methods of 1,5-dicarbonyl compounds reported in the literature, and the representative methods are: [0003] (1) 1,5-dicarbonyl compounds are synthesized from enoyl phosphonate and carbonyl xanthate through a free radical process, with a yield of 40-85% (see literature Org.Lett.2013, 15, 4818-4821 ). [0004] [0005] R = alkyl, aryl, Cl, CO 2 Et,P(O)(OEt) 2 , OPiv [0006] R'=H,CH 3 ,CO 2 Et [0007] X=CH 2 ,O,NTs [0008...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B37/06C07C67/333C07C69/738C07D307/12C07D213/55
Inventor 蔡桂鑫文静
Owner SOUTHWEST UNIV
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